TECHNICAL FIELD
[0001] The present invention relates to a laminated rubber hose comprising a fluororubber
and a silicone rubber.
BACKGROUND ART
[0002] For a rubber hose used as a component for automobiles or other industrial component,
various materials such as an acrylic rubber, a silicone rubber, an ethylene propylene
rubber and a fluororubber are employed. Among them, for a rubber hose for an intercooler
of a Diesel engine, the blow-by gas resistance is required. The blow-by gas is a high
temperature mixed gas comprising combustion gas, unburned gas, oil mist etc. emitted
from the engine. For a material which suits this application, the oil resistance,
the corrosive gas resistance, etc. are required in addition to the heat resistance.
A fluororubber is excellent in the heat resistance, the oil resistance, the chemical
resistance etc. and accordingly provides a rubber hose having excellent characteristics
suitable for the above application (for example, JP-A-2001-233918). However, a fluororubber
is expensive, and thus the cost of the rubber hose tends to be high, such being problematic.
[0003] It is an object of the present invention to provide a rubber hose which is excellent
in the blow-by gas resistance and is available at a low cost.
DISCLOSURE OF THE INVENTION
[0004] The present invention provides a laminated rubber hose comprising an inner layer
made of a fluororubber composition and an outer layer made of a silicone rubber composition,
co-vulcanized, wherein the peel strength between the inner layer and the outer layer
after the co-vulcanization is at least 8 N/cm.
[0005] Further, the present invention provides the above laminated rubber hose, wherein
the laminated rubber hose is a rubber hose for an intercooler of a Diesel engine.
BRIEF EXPLANATION OF THE DRAWINGS
[0006] Fig. 1 is a cross-sectional view illustrating a testing apparatus for the blow-by
gas resistance of a laminated rubber sheet.
[0007] Fig. 2 is a cross-sectional view illustrating a laminated rubber hose at the blow-by
gas resistance test. Explanation of Numerical References
- 1:
- vulcanized rubber sheet
- 2:
- stainless steel container
- 3:
- model liquid of blow-by gas
- 4:
- vulcanized rubber hose
- 5:
- stopper
- 6:
- rubber hose fastening plate
MODE FOR CARRYING OUT THE INVENTION
[0008] The fluororubber in the present invention may be an elastic copolymer of fluoromonomers
or an elastic copolymer of a fluoromonomer and a hydrocarbon monomer. The fluoromonomer
may, for example, be a fluoroethylene such as vinylidene fluoride, trifluoroethylene,
trifluorochloroethylene, tetrafluoroethylene or vinyl fluoride, a fluoropropylene
such as hexafluoropropylene or pentafluoropropylene, or a perfluoro(alkyl vinyl ether)
such as perfluoro(methyl vinyl ether) or perfluoro(propyl vinyl ether). The fluoromonomer
may be used alone, or two or more of them may be used in combination.
[0009] The hydrocarbon monomer may, for example, be an olefin such as ethylene or propylene,
a vinyl ether such as methyl vinyl ether or ethyl vinyl ether, a vinyl ester such
as vinyl acetate or an acrylate such as methyl acrylate. The hydrocarbon monomer may
be used alone, or two or more of them may be used in combination.
[0010] Further, in the present invention, as the fluororubber, a copolymer comprising the
above fluoromonomer and hydrocarbon monomer, and in addition, other monomer to be
a vulcanization site copolymerized therewith in a small amount, may also be used.
Said other monomer may be a monomer containing an iodine atom such as 2-iodoperfluoropropene
or 4-iodoperfluorobutene-1, or a monomer containing a bromine atom such as bromotrifluoroethylene
or 4-bromo-3,3,4,4-tetrafluorobutene-1.
[0011] Specific examples of the fluororubber in the present invention include a vinylidene
fluoride/hexafluoropropylene elastic copolymer, a vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene
elastic copolymer, a tetrafluoroethylene/propylene elastic copolymer and a tetrafluoroethylene/vinylidene
fluoride/propylene elastic copolymer. The fluororubber may be used alone, or two or
more of them may be used in combination. Among them, preferred is a tetrafluoroethylene/propylene
elastic copolymer or a tetrafluoroethylene/vinylidene fluoride/propylene elastic copolymer
excellent in the blow-by gas resistance.
[0012] As the method for vulcanizing the fluororubber in the present invention, vulcanization
with an organic peroxide, vulcanization with a polyol comprising a vulcanizing agent
such as bisphenol AF and a vulcanization aid such as a quaternary ammonium salt combined,
or vulcanization with an amine employing e.g. hexamethylenediamine dicarbamate may,
for example, be mentioned. Among them, vulcanization with an organic peroxide is preferred
since the vulcanized fluororubber will be excellent in the blow-by gas resistance.
[0013] In the present invention, in order to vulcanize the fluororubber with an organic
peroxide, it is preferred to introduce a vulcanization site to the fluororubber by
a method of e.g. copolymerizing a monomer containing an iodine atom or a bromine atom
to be a vulcanization site, adding a chain transfer agent containing an iodine atom
or a bromine atom such as 1,4-diiodoperfluorobutane or 1-bromo-4-iodoperfluorobutane
at the time of polymerization, or subjecting the fluororubber to an alkali treatment
or a heat treatment.
[0014] The silicone rubber in the present invention may, for example, be dimethyl silicone
rubber, methyl vinyl silicone rubber, methyl phenyl silicone rubber or fluorosilicone
rubber. Particularly preferred is dimethyl silicone rubber. As the method for vulcanizing
the silicone rubber, vulcanization with an organic peroxide is preferred.
[0015] In the present invention, it is preferred that the silicone rubber composition contains
cerium oxide, iron oxide or a mixture thereof. When cerium oxide, iron oxide or a
mixture thereof is contained, the laminated rubber hose will be excellent in the heat
aging resistance. The content of the cerium oxide, the iron oxide or the mixture thereof
is preferably from 0.1 to 10 parts by mass, more preferably from 0.5 to 5 parts by
mass per 100 parts by mass of the silicone rubber. When the content is within this
range, the laminated rubber hose will be excellent in the heat aging resistance, and
the peel strength between the inner layer made of the fluororubber composition and
the outer layer made of the silicone rubber composition, co-vulcanized, is less likely
to decrease for a long time even at a high temperature.
[0016] In the present invention, the co-vulcanization of the inner layer made of the fluororubber
composition and the outer layer made of the silicone rubber composition is preferably
vulcanization with an organic peroxide. A laminated rubber hose comprising a fluororubber
inner layer and a silicone rubber outer layer co-vulcanized with an organic peroxide
is particularly excellent in the blow-by gas resistance.
[0017] The organic peroxide to be used for the vulcanization with an organic peroxide may,
for example, be dibenzoyl peroxide, dicumyl peroxide, di(tert-butyl) peroxide, tert-butyl
peroxyacetate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxybenzoate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane,
2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, α,α'-bis(tert-butylperoxy)-p-diisopropylbenzene
or 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane. They may be used alone or two or more
of them may be used in combination.
[0018] The blending amount of the organic peroxide is preferably from 0.01 to 10 parts by
mass, more preferably from 0.1 to 5 parts by mass per 100 parts by mass of the fluororubber.
Further, it is preferably from 0.01 to 10 parts by mass, more preferably from 0.1
to 5 parts by mass per 100 parts by mass of the silicone rubber. Within this range,
the laminated rubber hose will be excellent in the adhesive force between the fluororubber
layer and the silicone rubber layer, and will be excellent in strength.
[0019] In the present invention, when the fluororubber composition and the silicone rubber
composition are co-vulcanized with an organic peroxide, a compound having at least
two unsaturated bonds in one molecule may be blended as a vulcanization aid. Said
compound may, for example, be triallyl cyanurate, triallyl isocyanurate, bismaleimide,
ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, trimethylolpropane
trimethacrylate or divinylbenzene. Among them, preferred is triallyl cyanurate or
triallyl isocyanurate. The blending amount of the vulcanization aid is preferably
from 0.1 to 10 parts by mass, more preferably from 0.5 to 7 parts by mass per 100
parts by mass of the fluororubber or the silicone rubber.
[0020] In the present invention, it is also preferred to blend a nitrogen-containing compound
such as an amine or an imine with the fluororubber composition. A laminated rubber
hose obtained by blending a nitrogen-containing compound will be excellent in the
adhesive force between the fluororubber inner layer and the silicone rubber outer
layer. Specific examples of the nitrogen-containing compound include 1,8-diazabicyclo[5.4.0]undecene-7,
1,5-diazabicyclo[4.3.0]nonene-5, 1,4-diazabicyclo[2.2.2]octane, triethylamine, tributylamine,
diphenylamine, piperidine, morpholine, pyridine, benzotriazole and p-dimethylaminopyridine.
The blending amount of the nitrogen-containing compound is preferably from 0.01 to
2 parts by mass, more preferably from 0.05 to 1 part by mass per 100 parts by mass
of the fluororubber.
[0021] In the present invention, with the fluororubber composition and the silicone rubber
composition, in addition to the above compounding agent, other compounding agent may
be blended as the case requires. Said other compounding agent may, for example, be
a filler, a processing aid, an adhesion aid or a pigment.
[0022] The filler may, for example, be carbon black, fumed silica, wet silica, fine quartz
powder, diatomaceous earth, zinc oxide, basic magnesium carbonate, activated calcium
carbonate, magnesium silicate, aluminum silicate, titanium dioxide, talc, mica powder,
aluminum sulfate, calcium sulfate, barium sulfate, asbestos, graphite, wollastonite,
molybdenum disulfide, carbon fiber, aramid fiber, whiskers and glass fiber.
[0023] The processing aid may, for example, be a fatty acid derivative such as sodium stearate
or amide stearate, natural wax or synthetic wax.
[0024] The adhesion aid may, for example, be a silane coupling agent or a titanate type
coupling agent.
[0025] As the method for producing the laminated rubber hose of the present invention, conventional
rubber processing method and molding method are employed. As a specific example, a
fluororubber or a silicone rubber and the above compounding agents are kneaded by
means of a conventional kneader such as a twin roll or a Banbury mixer to obtain a
fluororubber composition or a silicone rubber composition. Then, the obtained fluororubber
composition and silicone rubber composition are co-extruded to obtain a non-vulcanized
laminated rubber sheet. Then, the non-vulcanized laminated rubber sheet is superposed
by means of e.g. a tubular mandrel, followed by co-vulcanization under a pressure
of preferably from 0.2 to 10 MPa at a temperature of preferably from 100 to 300°C
to obtain a laminated rubber hose.
[0026] Otherwise, it is also preferred to co-extrude the fluororubber composition and the
silicone rubber composition to obtain a non-vulcanized laminated rubber hose, followed
by co-vulcanization under the same conditions as mentioned above to obtain a laminated
rubber hose. In such production methods, the inner layer made of the fluororubber
composition and the outer layer made of the silicone rubber composition are co-vulcanized
in direct contact with each other to obtain a multi-layer rubber hose.
[0027] Of the laminated rubber hose of the present invention, the peel strength between
the inner layer made of a fluororubber composition and the outer layer made of a silicone
rubber composition after the co-vulcanization is at least 8 N/cm. If the strength
is less than this value, the heat aging resistance of the peel strength between the
fluororubber layer and the silicone rubber layer of the laminated rubber hose is insufficient
as a rubber hose for an intercooler of a Diesel engine. It is preferably at least
10 N/cm. Further, the peel strength is more preferably at least 8 N/cm even after
heat aging at 200°C for 70 hours, most preferably at least 10 N/cm.
[0028] As the laminated rubber hose of the present invention, in addition to a two-layer
rubber hose comprising a vulcanized fluororubber inner layer and a vulcanized silicone
rubber outer layer, a multi-layer rubber hose structure such as a three-layer rubber
hose comprising a vulcanized fluororubber inner layer, a vulcanized silicone rubber
outer layer and a vulcanized silicone rubber outermost layer or a three-layer rubber
hose comprising a vulcanized fluororubber inner layer, a vulcanized silicone rubber
outer layer and a reinforced fiber layer may also be employed. It is preferred that
the vulcanized silicone rubber layer is reinforced by fibers. Further, usually the
vulcanized fluororubber layer and the vulcanized silicone rubber layer are directly
bonded by vulcanization, however, an adhesive layer such as a primer may be present
between the layers.
[0029] As the reinforcing fibers for the laminated rubber hose, aramid fibers, metaaramid
fibers may, for example, be mentioned. As commercial available products, Technora
(tradename, manufactured by TEIJIN LIMITED), Nomex (tradename, manufactured by DuPont)
may, for example, be mentioned.
[0030] Of the laminated rubber hose of the present invention, the thickness of the fluororubber
layer is preferably from 0.5 to 2 mm, more preferably from 0.8 to 1.5 mm. Further,
the thickness of the silicone rubber layer is preferably from 1 to 8 mm, more preferably
from 2 to 5 mm. The inner diameter of the rubber hose for an intercooler is preferably
from 30 to 200 mm, more preferably from 60 to 120 mm.
[0031] The blow-by gas resistance of the laminated rubber hose of the present invention
is preferably at most 50 mg/cm
2, more preferably at most 20 mg/cm
2, most preferably at most 10 mg/cm
2, as the mass of a model liquid which passed through the rubber hose per unit surface
area, as measured by a method of employing a model liquid as mentioned hereinafter.
[0032] The laminated rubber hose of the present invention is suitable for a rubber hose
for an intercooler of a Diesel engine. Further, its application may, for example,
be a rubber hose to be used for chemical plant equipment, food plant equipment, food
equipment, atomic power plant equipment, general industrial equipment etc., or a rubber
hose to be used for vehicle such as an automobile, a ship or an aircraft. Specific
examples include a steam resistant rubber hose, an oil resistant rubber hose, a combustion
gas resistant rubber hose, a break oil resistant rubber hose, a chemical resistant
rubber hose and a flon resistant rubber hose.
[0033] Now, the present invention will be specifically explained with reference to Examples,
however, the present invention is by no means restricted thereto.
EXAMPLES
Preparation of Non-Vulcanized Rubber Sheets of Fluororubbers 1 to 3 and Silicone Rubbers
1 and 2
[0034] A rubber and various compounding agents were uniformly kneaded in a blending formulation
as shown in Table 1 by mass ratio by means of a twin roll to prepare non-vulcanized
rubber sheets of non-vulcanized fluororubber compositions 1 to 3 and non-vulcanized
silicone rubber compositions 1 and 2. The thickness of the non-vulcanized rubber sheets
of the fluororubber compositions 1 to 3 was 1 mm, and the thickness of the non-vulcanized
rubber sheets of the silicone rubber compositions 1 and 2 was 3 mm.
[0035] Abbreviations in Table 1 are as follows. AFLAS 150E: tetrafluoroethylene/propylene
elastic copolymer (tradename for a fluororubber manufactured by Asahi Glass Company,
Limited), G902: vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene elastic
copolymer (fluororubber manufactured by DAIKIN INDUSTRIES, LTD.), KE582-U (silicone
rubber manufactured by Shin-Etsu Chemical Co., Ltd.), TAIC: triallyl isocyanurate
(manufactured by Nippon Kasei Chemical Co., Ltd.), Perkadox 14: α,α'-bis(tert-butyl
peroxy)-p-diisopropylbenzene(tradename, manufactured by Kayaku Akzo Corporation),
DBU: 1,8-diazabicyclo[5.4.0]undecene-7.
TABLE 1
| |
Fluoro-rubber composition 1 |
Fluoro-rubber composition 2 |
Fluoro-rubber composition 3 |
Silicone rubber composition 1 |
Silicone rubber composition 2 |
| AFLAS 150E |
100 |
100 |
|
|
|
| G902 |
|
|
100 |
|
|
| KE582-U |
|
|
|
100 |
100 |
| Na stearate |
1 |
1 |
1 |
|
|
| MT carbon |
30 |
30 |
30 |
|
|
| TAIC |
5 |
5 |
5 |
|
|
| Perkadox 14 |
1 |
1 |
1 |
1 |
1 |
| DBU |
|
0.2 |
|
|
|
| Cerium oxide |
|
|
|
|
1 |
Preparation of Laminated Rubber Sheet
[0036] The non-vulcanized rubber sheet of the fluororubber composition and the non-vulcanized
rubber sheet of the silicone rubber composition were superposed one on the other,
followed by press vulcanization at a temperature of 170°C under a pressure of 1 MPa
for 20 minutes to obtain a laminated rubber sheet.
Peel Test
[0037] The laminated rubber sheet was cut into a width of 1 cm, and subjected to a test
for determination of peel strength between the fluororubber layer and the silicone
rubber layer in accordance with JIS K6854-1973. In a case where the test sample was
a laminated rubber hose, a sample obtained by cutting the laminated rubber hose lengthwise
into a sheet was employed.
Blow-By Gas Resistance Test
Test Employing Laminated Rubber Sheet:
[0038] In a stainless steel container 2 having a diameter of 140 mm and a height of 280
mm as shown in Fig. 1, 1 kg of a mixed liquid of gas oil/Diesel oil (CF10W-30, manufactured
by Nisseki Mitsubishi Oil Corporation)/distilled water=45/45/10 (vol%) was put as
a model liquid 3 of blow-by gas, and the container was sealed with a laminated rubber
sheet 1 so that the fluororubber layer faced inside. Then, the sealed container was
heated in an oven of 125°C for 168 hours, and then the mass reduction amount of the
mixed liquid in the container was measured. The mass of the model liquid which passed
through the laminated rubber sheet per unit surface area was calculated from the mass
reduction amount. Further, after the test, the peel test of the laminated rubber sheet
used for the test was carried out. A small gas reduction amount indicates excellent
blow-by gas resistance (engine exhaust gas resistance).
Test Employing Laminated Rubber Hose:
[0039] As shown in Fig. 2, each end of a laminated rubber hose 4 (inner diameter: 50 mm)
was sealed with a stopper 5 so that the effective length of the rubber hose would
be 150 mm, and each edge of the vulcanized rubber hose was fixed by a hose fastening
plate 6. 250 g of the above model liquid 3 of blow-by gas was enclosed in the laminated
rubber hose 4. The laminated rubber hose 4 was put in an oven of 125°C and heated
for 168 hours, and then the mass reduction amount was measured and the peel test of
the laminated rubber hose 4 after the test was carried out in the same manner as mentioned
above.
Heat Aging Resistance Test:
[0040] The laminated rubber sheet was cut into a width of 1 cm and held in an oven of 200°C
for 70 hours, and then the peel test between the fluororubber layer and the silicone
rubber layer was carried out in the same manner as mentioned above.
EXAMPLES 1 to 3
[0041] Each of the non-vulcanized rubber sheets of the fluororubber compositions 1 to 3
and the non-vulcanized rubber sheet of the silicone rubber composition 1 were bonded
by vulcanization to prepare laminated rubber sheets. The thickness of the vulcanized
fluororubber layer was 1 mm, and the thickness of the vulcanized silicone rubber layer
was 3 mm. The laminated rubber sheets were subjected to the peel test between the
fluororubber layer and the silicone rubber layer. Further, the blow-by gas resistance
test of the laminated rubber sheets was carried out by using the apparatus as shown
in Fig. 1. Further, after the blow-by gas resistance test, the peel test of the laminated
rubber sheets after the test was carried out. The results are shown in Table 2.
COMPARATIVE EXAMPLE 1
[0042] By using a vulcanized fluororubber sheet having a thickness of 1 mm, obtained by
press vulcanization of the non-vulcanized rubber sheet of the fluororubber composition
3 at 170°C for 20 minutes, the blow-by gas resistance test was carried out. The result
is shown in Table 2.
COMPARATIVE EXAMPLE 2
[0043] By using a vulcanized silicone rubber sheet having a thickness of 3 mm, obtained
by press vulcanization of the non-vulcanized rubber sheet of the silicone rubber composition
1 at 170°C for 20 minutes, the blow-by gas resistance test was carried out. The result
is shown in Table 2.
TABLE 2
| |
Ex. 1 |
Ex. 2 |
Ex. 3 |
Comp. Ex. 1 |
Comp. Ex. 1 |
| Vulcanized rubber sheet |
Fluoro-rubber composition 1/ silicone rubber composition 1 |
Fluoro-rubber composition 2/ silicone rubber composition 1 |
Fluoro-rubber composition 3/ silicone rubber composition 1 |
Fluoro-rubber composition 3 |
Silicone rubber composition 1 |
| Initial peel strength (N/cm) |
18 |
24 |
15 |
- |
- |
| Mass reduction amount after blow-by gas resistance test (mg/cm2) |
3.5 |
3.2 |
3.2 |
3.2 |
162.5 |
| Peel strength after test (N/cm) |
18 |
23 |
12 |
- |
- |
EXAMPLES 4 to 6
[0044] Each of the fluororubber compositions 1, 2 and 3 and the silicone rubber composition
1, each obtained by kneading by a twin roll, were co-extruded by a coextruder to obtain
non-vulcanized laminated rubber sheets, and each of the non-vulcanized laminated rubber
sheets was superposed on a tubular mandrel, followed by steam vulcanization at 160°C
for 30 minutes to obtain laminated rubber hoses comprising an inner layer made of
a fluororubber and an outer layer made of a silicone rubber, having an outer diameter
of 58 mm and an inner diameter of 50 mm. The thickness of each of the inner layers
made of the vulcanized fluororubbers 1, 2 and 3 was 1 mm, and the thickness of the
outer layer made of the vulcanized silicone rubber 1 was 3 mm. The peel test, the
blow-by gas resistance test of the laminated rubber hose as shown in Fig. 2 and the
peel test of the laminated rubber hose after the test were carried out. The results
are shown in Table 3.
COMPARATIVE EXAMPLE 3
[0045] Using a non-vulcanized rubber sheet of the fluororubber composition 3 having a thickness
of 1 mm, vulcanization was carried out on a tubular mandrel in the same manner as
in Example 4 to obtain a vulcanized fluororubber hose having a thickness of 1 mm.
The blow-by gas resistance test and the peel test were carried out in the same manner
as in Example 4. The results are shown in Table 3.
TABLE 3
| |
Ex. 4 |
Ex. 5 |
Ex. 6 |
Comp. Ex. 3 |
| Vulcanized rubber hose |
Fluoro-rubber composition 1/ silicone rubber composition 1 |
Fluoro-rubber composition 2/ silicone rubber composition 1 |
Fluoro-rubber composition 3/ silicone rubber composition 1 |
Fluoro-rubber composition 3 |
| Initial peel strength (N/cm) |
17 |
22 |
14 |
- |
| Mass reduction amount after blow-by gas resistance test (mg/cm2) |
4.2 |
4.3 |
4.5 |
4.7 |
| Peel strength after test (N/cm) |
16 |
23 |
12 |
- |
EXAMPLES 7 and 8
[0046] The non-vulcanized rubber sheet of the fluororubber composition 2 and each of the
non-vulcanized rubber sheets of the silicone rubber compositions 1 and 2 were bonded
by vulcanization to prepare laminated rubber sheets. The thickness of the vulcanized
fluororubber layer was 1 mm, and the thickness of the vulcanized silicone rubber layer
was 3 mm. The laminated rubber sheets were subjected to the peel test between the
fluororubber layer and the silicone rubber layer and the heat aging resistance test.
The results are shown in Table 4.
TABLE 4
| |
Ex. 7 |
Ex. 8 |
| Vulcanized rubber sheet |
Fluororubber composition 2/ silicone rubber composition 2 |
Fluororubber composition 2/ silicone rubber composition 1 |
| Peel strength (N/cm) |
40.1 |
12.7 |
| Peel strength after heat aging test (N/cm) |
25.3 |
5.0 |
INDUSTRIAL APPLICABILITY
[0047] The laminated rubber hose of the present invention is excellent in the peel strength
between the fluororubber layer and the silicone rubber layer, and is excellent in
the blow-by gas resistance (engine exhaust gas resistance). Further, it is excellent
also in the heat resistance, the oil resistance and the chemical resistance, and thus
it is useful for an application to e.g. a rubber hose for an intercooler of a Diesel
engine.